Amperometric detection of peroxides using peroxidase and porphyrin biomimetic modified electrodes

Biosensors designed with crosslinked redox hydrogel and horseradish peroxidase have been evaluated in aqueous and nonaqueous media. Electrodes made of a single layer of active material were prepared with Os(byp)2ClPyCH2 NHPoly(allylamine) polymer, (PAA-Os), attached to the enzyme by PEG-400 bifuncti...

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Autores principales: Baldini, E., Dall'Orto, V.C., Danilowicz, C., Rezzano, I., Calvo, E.J.
Formato: JOUR
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HRP
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_10400397_v14_n17_p1157_Baldini
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spelling todo:paper_10400397_v14_n17_p1157_Baldini2023-10-03T15:57:40Z Amperometric detection of peroxides using peroxidase and porphyrin biomimetic modified electrodes Baldini, E. Dall'Orto, V.C. Danilowicz, C. Rezzano, I. Calvo, E.J. Biomimetic Biosensor Enzyme HRP Peroxide Porphyrin lauric acid osmium peroxide polymer porphyrin amperometric biosensor aqueous solution article biomimetics chemical modification cross linking electrode hydrogen bond molecular stability oxidation reduction reaction polymerization quantitative analysis Biosensors designed with crosslinked redox hydrogel and horseradish peroxidase have been evaluated in aqueous and nonaqueous media. Electrodes made of a single layer of active material were prepared with Os(byp)2ClPyCH2 NHPoly(allylamine) polymer, (PAA-Os), attached to the enzyme by PEG-400 bifunctional reagent with the Os sites acting as electron wires. The electrodes proved to be stable in the presence of organic solvent considering the time evolution of the redox charge and the catalytic current. However, a reasonable decrease in the enzyme response is apparent while increasing solvent content in solution for detection of hydrogen and lauroyl peroxide. As an alternative biomimetic strategy, electrodes were modified with consecutive layers of PAA-Os and electropolymerized Fe-protoporphyrin IX. The electrochemical detection of peroxides was also possible with this system, proving that the poly[Fe-protoporphyrin IX]/Osmium complex system can mimic the peroxidase activity towards hydrogen and organic peroxides. The replacement of Fe-protoporphyrin by Ni-protoporphyrin IX and PAA-Os by PAA in different experiments demonstrates that the mechanism for peroxide reduction involves both Os and Fe-protoporphyrin IX sites. The enzymatic electrodes were applied to benzoyl peroxide quantitation in a pharmaceutical product. The method validation demonstrates that a simple and rapid FIA detection can be applied. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_10400397_v14_n17_p1157_Baldini
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Biomimetic
Biosensor
Enzyme
HRP
Peroxide
Porphyrin
lauric acid
osmium
peroxide
polymer
porphyrin
amperometric biosensor
aqueous solution
article
biomimetics
chemical modification
cross linking
electrode
hydrogen bond
molecular stability
oxidation reduction reaction
polymerization
quantitative analysis
spellingShingle Biomimetic
Biosensor
Enzyme
HRP
Peroxide
Porphyrin
lauric acid
osmium
peroxide
polymer
porphyrin
amperometric biosensor
aqueous solution
article
biomimetics
chemical modification
cross linking
electrode
hydrogen bond
molecular stability
oxidation reduction reaction
polymerization
quantitative analysis
Baldini, E.
Dall'Orto, V.C.
Danilowicz, C.
Rezzano, I.
Calvo, E.J.
Amperometric detection of peroxides using peroxidase and porphyrin biomimetic modified electrodes
topic_facet Biomimetic
Biosensor
Enzyme
HRP
Peroxide
Porphyrin
lauric acid
osmium
peroxide
polymer
porphyrin
amperometric biosensor
aqueous solution
article
biomimetics
chemical modification
cross linking
electrode
hydrogen bond
molecular stability
oxidation reduction reaction
polymerization
quantitative analysis
description Biosensors designed with crosslinked redox hydrogel and horseradish peroxidase have been evaluated in aqueous and nonaqueous media. Electrodes made of a single layer of active material were prepared with Os(byp)2ClPyCH2 NHPoly(allylamine) polymer, (PAA-Os), attached to the enzyme by PEG-400 bifunctional reagent with the Os sites acting as electron wires. The electrodes proved to be stable in the presence of organic solvent considering the time evolution of the redox charge and the catalytic current. However, a reasonable decrease in the enzyme response is apparent while increasing solvent content in solution for detection of hydrogen and lauroyl peroxide. As an alternative biomimetic strategy, electrodes were modified with consecutive layers of PAA-Os and electropolymerized Fe-protoporphyrin IX. The electrochemical detection of peroxides was also possible with this system, proving that the poly[Fe-protoporphyrin IX]/Osmium complex system can mimic the peroxidase activity towards hydrogen and organic peroxides. The replacement of Fe-protoporphyrin by Ni-protoporphyrin IX and PAA-Os by PAA in different experiments demonstrates that the mechanism for peroxide reduction involves both Os and Fe-protoporphyrin IX sites. The enzymatic electrodes were applied to benzoyl peroxide quantitation in a pharmaceutical product. The method validation demonstrates that a simple and rapid FIA detection can be applied.
format JOUR
author Baldini, E.
Dall'Orto, V.C.
Danilowicz, C.
Rezzano, I.
Calvo, E.J.
author_facet Baldini, E.
Dall'Orto, V.C.
Danilowicz, C.
Rezzano, I.
Calvo, E.J.
author_sort Baldini, E.
title Amperometric detection of peroxides using peroxidase and porphyrin biomimetic modified electrodes
title_short Amperometric detection of peroxides using peroxidase and porphyrin biomimetic modified electrodes
title_full Amperometric detection of peroxides using peroxidase and porphyrin biomimetic modified electrodes
title_fullStr Amperometric detection of peroxides using peroxidase and porphyrin biomimetic modified electrodes
title_full_unstemmed Amperometric detection of peroxides using peroxidase and porphyrin biomimetic modified electrodes
title_sort amperometric detection of peroxides using peroxidase and porphyrin biomimetic modified electrodes
url http://hdl.handle.net/20.500.12110/paper_10400397_v14_n17_p1157_Baldini
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AT danilowiczc amperometricdetectionofperoxidesusingperoxidaseandporphyrinbiomimeticmodifiedelectrodes
AT rezzanoi amperometricdetectionofperoxidesusingperoxidaseandporphyrinbiomimeticmodifiedelectrodes
AT calvoej amperometricdetectionofperoxidesusingperoxidaseandporphyrinbiomimeticmodifiedelectrodes
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